WO2017160845A1 - Compositions durcissables par un rayonnement pour la fabrication additive présentant une ténacité améliorée et une résistance à la température élevée - Google Patents

Compositions durcissables par un rayonnement pour la fabrication additive présentant une ténacité améliorée et une résistance à la température élevée Download PDF

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WO2017160845A1
WO2017160845A1 PCT/US2017/022311 US2017022311W WO2017160845A1 WO 2017160845 A1 WO2017160845 A1 WO 2017160845A1 US 2017022311 W US2017022311 W US 2017022311W WO 2017160845 A1 WO2017160845 A1 WO 2017160845A1
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Prior art keywords
radiation curable
additive fabrication
curable composition
mol
toughenable
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PCT/US2017/022311
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English (en)
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Luke KWISNEK
Brad SEURER
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Dsm Ip Assets B.V.
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Priority to KR1020187029537A priority Critical patent/KR102427130B1/ko
Priority to JP2018544303A priority patent/JP6798071B2/ja
Priority to CN201780017178.9A priority patent/CN108778688B/zh
Priority to US16/084,645 priority patent/US20190077073A1/en
Priority to EP17717919.9A priority patent/EP3429833B1/fr
Publication of WO2017160845A1 publication Critical patent/WO2017160845A1/fr
Priority to US17/580,747 priority patent/US20220134641A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264—Arrangements for irradiation
    • B29C64/268—Arrangements for irradiation using laser beams; using electron beams [EB]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264—Arrangements for irradiation
    • B29C64/277—Arrangements for irradiation using multiple radiation means, e.g. micromirrors or multiple light-emitting diodes [LED]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/386—Data acquisition or data processing for additive manufacturing
    • B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds

Definitions

  • the present invention relates to radiation curable compositions for additive fabrication with improved toughness, and their application in additive fabrication processes.
  • Additive fabrication processes for producing three dimensional objects are well known. Additive fabrication processes utilize computer-aided design (CAD) data of an object to build three- dimensional parts. These three-dimensional parts may be formed from liquid resins, powders, or other materials.
  • CAD computer-aided design
  • SL stereolithography
  • Stereolithography is a well-known process for rapidly producing models, prototypes, patterns, and production parts in certain applications.
  • SL uses CAD data of an object wherein the data is transformed into thin cross-sections of a three-dimensional object.
  • the data is loaded into a computer which controls a laser that traces a pattern of a cross section through a liquid radiation curable resin composition contained in a vat, solidifying a thin layer of the resin corresponding to the cross section.
  • the solidified layer is recoated with resin and the laser traces another cross section to harden another layer of resin on top of the previous layer.
  • the process is repeated layer by layer until the three-dimensional object is completed.
  • the three- dimensional object When initially formed, the three- dimensional object is, in general, not fully cured, and is called a "green model.” Although not required, the green model may be subjected to post-curing to enhance the mechanical properties of the finished part.
  • An example of an SL process is described in U.S. Patent No. 4,575,330.
  • lasers used in stereolithography traditionally ranging from 193 nm to 355 nm in wavelength, although other wavelength variants exist.
  • the use of gas lasers to cure liquid radiation curable resin compositions is well known.
  • the delivery of laser energy in a stereolithography system can be Continuous Wave (CW) or Q-switched pulses.
  • CW lasers provide continuous laser energy and can be used in a high speed scanning process.
  • their output power is limited which reduces the amount of curing that occurs during object creation. As a result the finished object will need additional post process curing.
  • excess heat could be generated at the point of irradiation which may be detrimental to the resin.
  • the use of a laser requires scanning point by point on the resin which can be time-consuming.
  • LEDs are semiconductor devices which utilize the phenomenon of electroluminescence to generate light.
  • LED UV light sources currently emit light at wavelengths between 300 and 475 nm, with 365 nm, 390 nm, 395 nm, 405 nm, and 415 nm being common peak spectral outputs. See textbook, "Light-Emitting Diodes” by E. Fred Schubert, 2 nd Edition, ⁇ E. Fred Schubert 2006, published by Cambridge University Press, for a more in-depth discussion of LED UV light sources.
  • green strength constitutes an important property of the green model and is determined essentially by the nature of the radiation curable composition employed in combination with the type of apparatus used and degree of exposure provided during part fabrication.
  • Other important properties of such compositions include a high sensitivity for the radiation employed in the course of curing and a minimum amount of curl or shrinkage
  • the radiation curable compositions used in additive manufacturing processes are capable of imparting robust mechanical properties such as strength, toughness and heat resistance, into the three-dimensional parts cured therefrom.
  • Toughness is the extent to which a certain material, when stressed, is able to absorb energy and plastically deform without fracturing. It can be measured in several ways under different stress conditions, and may vary for a given material depending on the axis through which a stress is applied. Generally speaking, in order to possess sufficient toughness, a material should be both strong and ductile. Strength or ductility alone does not necessarily render a materials tough. Certain high-strength but brittle materials, such as ceramics, are not typically considered to be tough. Conversely, high- ductility but weak materials such as many rubbers are also do not possess significant toughness. To be tough, therefore, a material should be able to withstand both high stresses and high strains.
  • the parts created via additive fabrication processes are required to possess a significant toughness.
  • Certain standardized methods which are used widely for evaluating the relative toughness of materials, especially for those cured via additive fabrication processes, include the Young's modulus of elasticity, elongation at break, as well as the Charpy and Izod impact tests.
  • the Young's modulus of elasticity and elongation at break tend to approximates toughness in the form of resilience over a relatively longer time period, whereas the Charpy and Izod impact tests are considered to be a better proxy for toughness under conditions in which a shock is imparted over a shorter time period.
  • thermoset plastics such as those formed from radiation curable compositions for additive fabrication
  • injection molded engineering plastics which are made from thermoplastic polymers.
  • the degree to which a radiation curable (i.e. thermoset) material is able to withstand heat is often characterized in the additive manufacturing industry by such material's heat deflection temperature (HDT).
  • HDT is the temperature at which a sample of the cured material deforms by a fixed distance under a specified load. It gives an indication of how the material behaves when stressed at elevated temperatures.
  • the ultimate HDT for radiation curable thermoset materials is determined by a number of factors, including the polymer network's crosslink density, its chemical structure, the type of tougheners/fillers employed, and the degree of cure.
  • a high HDT is important because it signals that a material is able to retain a high degree of its maximum strength even at elevated temperatures.
  • Crosslink density can be defined as the number of effective crosslinks per unit volume of the cured polymer.
  • crosslink density modifications there exists a well-known inverse relationship between toughness and heat resistance. That is, as crosslink density increases, a thermoset material's HDT increases, but its toughness concomitantly decreases. Conversely, as the cross-link density decreases, the toughness increases but HDT performance is known to suffer.
  • a discussion of the effects of modification of cross-link density in thermoset resins is discussed in, e.g., pp. 8-10 of "Handbook of Thermoset Plastics", Third Edition (Edited by Hanna Dodiuk and Sidney H. Goodman).
  • liquid radiation curable compositions are of particular importance in many additive fabrication processes, such as vat-based processes like stereolithography as described above.
  • Many additives or constituents of the composition which might improve the toughness or HDT of the three-dimensional parts cured therefrom make such existing liquid radiation curable resins are highly viscous; that is, they are sufficiently flow-resistant such that they will not readily form a smooth layer of liquid photocurable resin over the just formed solid layer to ensure accurate cure by actinic radiation.
  • highly viscous resins forming a new layer of liquid photocurable resin over the top of a previously-cured layer becomes a time consuming process.
  • Other concerns with regards to high viscosity liquid radiation curable compositions for additive fabrication processes such as stereolithography are described in, e.g. US20150044623, assigned to DSM IP Assets, B.V.
  • a first aspect of the claimed invention is a radiation curable composition for additive fabrication with improved toughness comprising:
  • a rubber toughenable base resin further comprising
  • liquid phase-separating toughening agent is present in an amount, relative to the weight of the rubber toughenable base resin, in a ratio from about 1 : 99 to about 1 :3, more preferably about 1 :99 to about 1 :4, more preferably about 1 :99 to about 1 :9, more preferably about 1 :50 to about 1 : 12, more preferably about 1 : 19; and
  • the average molecular weight between crosslinks (Mc) of the rubber toughenable base resin is greater than 130 g/mol, more preferably greater than 150 g/mol; in another embodiment more preferably greater than 160 g/mol; and in another embodiment greater than 180 g/mol.
  • a second aspect of the claimed invention is a radiation curable composition for additive fabrication with improved toughness comprising:
  • a rubber toughenable base resin further comprising
  • liquid phase-separating toughening agent a liquid phase-separating toughening agent; wherein the liquid phase-separating toughening agent is an epoxidized pre-reacted hydrophobic macromolecule.
  • a third aspect of the claimed invention is a process of forming a three-dimensional object comprising the steps of forming and selectively curing a liquid layer of the radiation curable composition for additive fabrication with improved toughness according to either the first or second aspects of the claimed invention with actinic radiation and repeating the steps of forming and selectively curing the liquid layer of the radiation curable composition for additive fabrication according to the first or second aspects of the claimed invention a plurality of times to obtain a three-dimensional object.
  • a fourth aspect of the claimed invention is the three-dimensional object formed by the process according to the third aspect of the claimed invention from the radiation curable composition for additive fabrication with improved toughness according to either the first or second aspects of the claimed invention.
  • a first aspect of the claimed invention is a radiation curable composition for additive fabrication with improved toughness comprising:
  • a rubber toughenable base resin further comprising
  • liquid phase-separating toughening agent is present in an amount, relative to the weight of the rubber toughenable base resin, in a ratio from about 1 : 99 to about 1 :3, more preferably about 1 :99 to about 1 :4, more preferably about 1 :99 to about 1 :9, more preferably about 1 :50 to about 1 : 12, more preferably about 1 : 19%; and wherein the average molecular weight between crosslinks (Mc) of the rubber toughenable base resin is greater than 130 g/mol, more preferably greater than 150 g/mol; in another embodiment more preferably greater than 160 g/mol; and in another embodiment greater than 180 g/mol.
  • All embodiments of radiation curable compositions with improved toughness for additive fabrication according to the present invention possess, as at least a constituent part, a rubber toughenable base resin.
  • This base resin forms a polymer matrix within which toughening agents, which themselves can be liquid and soluble in the base resin prior to curing, phase separate forming domains from the surrounding polymer network of the base resin during the curing process.
  • a rubber toughenable base resin on its own, sufficiently enables the creation of three dimensional parts via an additive fabrication process, the three-dimensional parts created therefrom may lack the requisite toughness to be considered suitable for many end-use applications.
  • "rubber toughenable” does not require that rubbers explicitly be used to toughen the base resin; rather, it merely signifies that such resins are able to be toughened by virtue of a soft-phase separation mechanism.
  • Rubber toughenable base resins according to the present invention may possess sub- constituents divided into five potential categories: optionally, at least one cationically
  • the rubber toughenable base resin comprises at least one cationically polymerizable component; that is a component which undergoes polymerization initiated by cations or in the presence of acid generators.
  • the cationically polymerizable component is a component which undergoes polymerization initiated by cations or in the presence of acid generators.
  • Suitable cyclic ether compounds can comprise cyclic ether groups as side groups or groups that form part of an alicyclic or heterocyclic ring system.
  • the cationic polymerizable component is selected from the group consisting of cyclic ether compounds, cyclic acetal compounds, cyclic thioethers compounds, spiro-orthoester compounds, cyclic lactone compounds, and vinyl ether compounds, and any combination thereof.
  • Suitable cationically polymerizable components include cyclic ether compounds such as epoxy compounds and oxetanes, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds, and vinylether compounds.
  • cationically polymerizable components include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resins, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether,
  • the cationically polymerizable component may optionally also contain polyfunctional materials including dendritic polymers such as dendrimers, linear dendritic polymers, dendrigraft polymers, hyperbranched polymers, star branched polymers, and hypergraft polymers with epoxy or oxetane functional groups.
  • dendritic polymers may contain one type of polymerizable functional group or different types of polymerizable functional groups, for example, epoxy and oxetane functions.
  • the rubber toughenable base resin of the present invention also or instead comprises one or more mono or poly glycidylethers of aliphatic alcohols, aliphatic polyols, polyesterpolyols or polyetherpolyols.
  • preferred components include 1,4- butanedioldiglycidylether, glycidylethers of polyoxyethylene and polyoxypropylene glycols and triols of molecular weights from about 200 to about 10,000; glycidylethers of polytetramethylene glycol or poly(oxyethylene-oxybutylene) random or block copolymers.
  • the cationically polymerizable component comprises a polyfunctional glycidylether that lacks a cyclohexane ring in the molecule.
  • the cationically polymerizable component includes a neopentyl glycol diglycidyl ether.
  • the cationically polymerizable component includes a 1,4 cyclohexanedimethanol diglycidyl ether.
  • ErisysTM GE 22 ErisysTM products are available from Emerald Performance MaterialsTM
  • HeloxyTM modifiers are available from Momentive Specialty Chemicals
  • Grilonit® F713 examples of commercially available preferred monofunctional glycidylethers are HeloxyTM 71, HeloxyTM 505, HeloxyTM 7, HeloxyTM 8, and HeloxyTM 61.
  • the epoxide is 3,4-epoxycyclohexylmethyl-3',4- epoxycyclohexanecarboxylate (available as CELLOXIDETM 202 IP from Daicel Chemical, or as CYRACURETM UVR-6105 from Dow Chemical), hydrogenated bisphenol A-epichlorohydrin based epoxy resin (available as EPONTM 1510 from Momentive), 1,4-cyclohexanedimethanol diglycidyl ether (available as HELOXYTM 107 from Momentive), a hydrogenated bisphenol A diglycidyl ether (available as EPONTM 825 from Momentive), and any combination thereof.
  • CELLOXIDETM 202 IP from Daicel Chemical, or as CYRACURETM UVR-6105 from Dow Chemical
  • hydrogenated bisphenol A-epichlorohydrin based epoxy resin available as EPONTM 1510 from Momentive
  • 1,4-cyclohexanedimethanol diglycidyl ether available as HELOXYTM 107
  • the above-mentioned cationically polymerizable compounds can be used singly or in combination of two or more thereof.
  • the cationic polymerizable component further comprises at least two different epoxy components.
  • the cationic polymerizable component includes a cycloaliphatic epoxy, for example, a
  • the cationic polymerizable component includes an epoxy having an aromatic or aliphatic glycidyl ether group with 2 (difunctional) or more than 2 (polyfunctional) epoxy groups.
  • the rubber toughenable base resin does not contain a cationic polymerizable component at all.
  • the rubber toughenable base resin can therefore include suitable amounts of the cationic polymerizable component, for example, in certain embodiments, in an amount from about 0 wt% to about 85% by weight of the rubber toughenable base resin, in further embodiments from about 35 wt% to about 75 wt%, and in further embodiments from about 35 wt% to about 65 wt% of the rubber toughenable base resin.
  • the cationically polymerizable component also includes one or more oxetanes.
  • the cationic polymerizable component includes an oxetane, for example, an oxetane containing 1, 2 or more than 2 oxetane groups. If utilized in the composition, the oxetane component is present in a suitable amount from about 5 to about 30 wt% of the rubber toughenable base resin.
  • the oxetane component is present in an amount from about 10 to about 25 wt% of the rubber toughenable base resin, and in yet another embodiment, the oxetane component is present in an amount from 15 to about 20 wt% of the rubber toughenable base resin.
  • the rubber toughenable base resin comprises at least one free-radical polymerizable component, that is, a component which undergoes polymerization initiated by free radicals.
  • the free-radical polymerizable components are monomers, oligomers, and/or polymers; they are monofunctional or polyfunctional materials, i.e., have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10...20...30...40...50... 100, or more functional groups that can polymerize by free radical initiation, may contain aliphatic, aromatic, cycloaliphatic, arylaliphatic, heterocyclic moiety(ies), or any combination thereof.
  • polyfunctional materials include dendritic polymers such as dendrimers, linear dendritic polymers, dendrigraft polymers, hyperbranched polymers, star branched polymers, and hypergraft polymers; see, e.g., US
  • the dendritic polymers may contain one type of polymerizable functional group or different types of polymerizable functional groups, for example, acrylates and methacrylate functions.
  • Examples of free-radical polymerizable components include acrylates and methacrylates such as isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloyl morpholine, (meth)acrylic acid, 2- hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (
  • (meth)acrylate ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, beta-carboxyethyl (meth)acrylate, phthalic acid (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, butylcarbamylethyl (meth)acrylate, n-isopropyl (meth)acryl amide fluorinated (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate.
  • poly functional free-radical polymerizable components include those with (meth)acryloyl groups such as trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, ethylene glycol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, dicyclopentadiene dimethanol di(meth)acrylate, [2-[l, l-dimethyl-2-[(l-oxoallyl)oxy]ethyl]-5-ethyl-l,3-dioxan-5- yljmethyl acrylate; 3,9-bis(l, l-dimethyl-2-hydroxyethyl)-2,4,8, 10-tetraoxaspiro[5.5]undecane di(meth)acrylate; dipentaerythritol monohydroxypenta(meth)acrylate, propoxylated
  • tri(meth)acrylate pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)crylate, tricyclodecane diyl dimethyl di(meth)acrylate and alkoxylated versions (e.g., ethoxylated and/or propoxylated) of any of the preceding monomers, and also di(meth)acrylate of a diol which is an ethylene oxide or propylene oxide adduct to bisphenol A, di(meth)acrylate of a diol which is an ethylene oxide or propylene oxide adduct to hydrogenated bisphenol A, epoxy (meth)acrylate which is a (meth)acrylate adduct to bisphenol A of diglycidyl ether, diacrylate of polyoxy alkylated bisphenol A, and triethylene glycol divinyl ether, and adducts of hydroxy ethyl acrylate.
  • the radically polymerizable component is a polyfunctional (meth)acrylate.
  • the polyfunctional (meth)acrylates may include all methacryloyl groups, all acryloyl groups, or any combination of methacryloyl and acryloyl groups.
  • the free-radical polymerizable component is selected from the group consisting of bisphenol A diglycidyl ether di(meth)acrylate, ethoxylated or propoxylated bisphenol A or bisphenol F di(meth)acrylate, dicyclopentadiene dimethanol di(meth)acrylate, [2-[l,l-dimethyl-2- [(1 -oxoallyl)oxy] ethyl] -5-ethyl- 1 , 3 -dioxan-5 -yl] methyl acrylate, dipentaerythritol
  • the polyfunctional (meth)acrylate has more than 2, more preferably more than 3, and more preferably greater than 4 functional groups.
  • the radically polymerizable component consists exclusively of a single polyfunctional (meth)acrylate component.
  • the exclusive radically polymerizable component is tetra-functional, in further embodiments, the exclusive radically polymerizable component is penta-functional, and in further embodiments, the exclusive radically polymerizable component is hexa-functional.
  • the free-radical polymerizable component is selected from the group consisting of bisphenol A diglycidyl ether diacrylate, dicyclopentadiene dimethanol diacrylate, [2- [ 1 , 1 -dimethyl-2- [( 1 -oxoallyl)oxy]ethyl]-5 -ethyl- 1 , 3 -dioxan-5 -yl] methyl aery late, dipentaerythritol monohydroxypentaacrylate, propoxylated trimethylolpropane triacrylate, and propoxylated neopentyl glycol diacrylate, and any combination thereof.
  • the rubber toughenable base resin of the invention includes one or more of bisphenol A diglycidyl ether di(meth)acrylate, dicyclopentadiene dimethanol di(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, propoxylated
  • trimethylolpropane tri(meth)acrylate, and/or propoxylated neopentyl glycol di(meth)acrylate and more specifically one or more of bisphenol A diglycidyl ether diacrylate, dicyclopentadiene dimethanol diacrylate, dipentaerythritol pentaacrylate, propoxylated trimethylolpropane triacrylate, and/or propoxylated neopentyl glycol diacrylate.
  • the above-mentioned radically polymerizable compounds can be used singly or in combination of two or more thereof.
  • the rubber toughenable base resin can include any suitable amount of the free-radical polymerizable components, for example, in certain embodiments, in an amount up to about 40 wt% of the composition, in certain embodiments, from about 2 to about 40 wt% of the composition, in other embodiments from about 5 to about 30 wt%, and in further embodiments from about 10 to about 20 wt% of the composition.
  • the rubber toughenable base resin can include up to 95 wt% of one or more radically polymerizable components.
  • the rubber toughenable base resins of the present invention also include a
  • the photoinitiating system can include a free-radical photoinitiator and/or a cationic photoinitiator.
  • the radiation curable composition includes a photoinitiating system contains at least one photoinitiator having a cationic initiating function, and at least one photoinitiator having a free radical initiating function.
  • the photoinitiating system can include a photoinitiator that contains both free-radical initiating function and cationic initiating function on the same molecule.
  • the photoinitiating system includes one or more free-radical photoinitiators and no cationic photoinitiators.
  • the photoinitiator is a compound that chemically changes due to the action of light or the synergy between the action of light and the electronic excitation of a sensitizing dye to produce at least one of a radical, an acid, and a base.
  • the rubber toughenable base resin includes a cationic photoinitiator.
  • Cationic photoinitiators initiate cationic ring-opening polymerization upon irradiation of light.
  • a sulfonium salt photoinitiator is used, for example, dialkylphenacylsulfonium salts, aromatic sulfonium salts, triaryl sulfonium salts, and any combination thereof.
  • the rubber toughenable base resin includes a cationic photoinitiator.
  • the cationic photoinitiator initiates cationic ring-opening polymerization upon irradiation of light.
  • any suitable cationic photoinitiator can be used, for example, those with cations selected from the group consisting of onium salts, halonium salts, iodosyl salts, selenium salts, sulfonium salts, sulfoxonium salts, diazonium salts, metallocene salts,
  • di(cyclopentadienyliron)arene salt compounds di(cyclopentadienyliron)arene salt compounds, and pyridinium salts, and any combination thereof.
  • the cation of the cationic photoinitiator is selected from the group consisting of aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene based compounds, aromatic phosphonium salts, and any combination thereof.
  • the cation is a polymeric sulfonium salt, such as in US5380923 or
  • the cationic photoinitiator is selected from the group consisting of triarylsulfonium salts, diaryliodonium salts, and metallocene based compounds, and any combination thereof.
  • Onium salts e.g., iodonium salts and sulfonium salts, and ferrocenium salts, have the advantage that they are generally more thermally stable.
  • the cationic photoinitiator has an anion selected from the group consisting of BF 4 " , AsFe “ , SbFe “ , PF 6 “ , [B(CF 3 ) 4 ] “ , B(C 6 F 5 )4 “ , B[C 6 H 3 -3,5(CF 3 )2]4 " ,
  • the cationic photoinitiator has a cation selected from the group consisting of aromatic sulfonium salts, aromatic iodonium salts, and metallocene based compounds with at least an anion selected from the group consisting of SbF6 ⁇ , PF6 ⁇ , B(C6F 5 )4 ⁇ , [B(CF 3 )4] " , tetrakis(3,5-difluoro-4-methoxyphenyl)borate, perfluoroalkylsulfonates, perfluoroalkylphosphates, tris[(perfluoroalkyl)sulfonyl]methides, and [(C2F5) 3 PF 3 ] " .
  • Examples of cationic photoinitiators useful for curing at 300-475 nm, particularly at 365 nm UV light, without a sensitizer include 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4- fluorophenyl)sulfonium hexafluoroantimonate, 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4- fluorophenyl)sulfonium tetrakis(pentafluorophenyl)borate, 4-[4-(3- chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium tetrakis(3,5-difluoro-4- methyloxyphenyl)borate, 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)
  • Preferred cationic photoinitiators include, either alone or in a mixture: bis[4- diphenylsulfoniumphenyl] sulfide bishexafluoroantimonate; thiophenoxyphenylsulfonium hexafluoroantimonate (available as Chivacure 1 176 from Chitec), tris(4-(4- acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate (Irgacure® PAG 290 from BASF), tris(4-(4-acetylphenyl)thiophenyl)sulfonium tris[(trifluoromethyl)sulfonyl]methide (Irgacure® GSID 26-1 from BASF), and tris(4-(4-acetylphenyl)thiophenyl)sulfonium hexafluoro
  • the liquid radiation curable resin composition for additive fabrication may be irradiated by laser or LED light operating at any wavelength in either the UV or visible light spectrum.
  • the irradiation is from a laser or LED emitting a wavelength of from 340 nm to 415 nm.
  • the laser or LED source emits a peak wavelength of about 340 nm, 355 nm, 365 nm, 375 nm, 385 nm, 395 nm, 405 nm, or 415 nm.
  • the rubber toughenable base resin comprises an aromatic triaryl sulfonium salt cationic photoinitiator.
  • Triarylsulfonium salts Ar3S + MXn " with complex metal halide anions such as BF4 ⁇ , AsF 6 " , PF 6 “ , and SbF 6 " , are disclosed in J Polymr Sci, Part A (1996), 34(16), 3231-3253.
  • aromatic triaryl sulfonium salts as the cationic photoinitiator in radiation curable resins is desirable in additive fabrication processes because the resulting resin attains a fast photospeed, good thermal-stability, and good photo-stability.
  • the cationic photoinitiator is an aromatic triaryl sulfonium salt that is more specifically an R-substituted aromatic thioether triaryl sulfonium
  • tetrakis(pentafluorophenyl)borate cationic photoinitiator is tris(4-(4- acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate.
  • Tris(4-(4- acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate is known commercially as IRGACURE® PAG-290 and is available from Ciba/BASF.
  • the cationic photoinitiator is an aromatic triaryl sulfonium salt that possesses an anion represented by SbF 6 ⁇ , PF 6 ⁇ , BF4 ⁇ , (CF 3 CF2) 3 PF 3 ⁇ , (CeFs ⁇ B-,
  • a particularly preferred aromatic triaryl sulfonium cationic photoinitiator has an anion that is a fluoroalkyl-substituted fluorophosphate.
  • an aromatic triaryl sulfonium cationic photoinitiator having a fluoroalkyl-substituted fluorophosphate anion is the CPI- 200 series (for example CPI-200K® or CPI-210S®) or 300 series, available from San-Apro
  • the rubber toughenable base resin can include any suitable amount of the cationic photoinitiator, for example, in certain embodiments, from 0% to about 15% by weight of the rubber toughenable base resin, in certain embodiments, up to about 5% by weight of the rubber
  • the toughenable base resin and in further embodiments from about 2% to about 10% by weight of the rubber toughenable base resin, and in other embodiments, from about 0.1% to about 5% by weight of the rubber toughenable base resin.
  • the amount of cationic photoinitiator is from about 0.2 wt% to about 4 wt% of the rubber toughenable base resin, and in other
  • the rubber toughenable base resin may include a photosensitizer.
  • photo sensitizer is used to refer to any substance that either increases the rate of photoinitiated polymerization or shifts the wavelength at which polymerization occurs; see textbook by G. Odian, Principles of
  • photosensitizers include heterocyclic and fused-ring aromatic hydrocarbons, organic dyes, and aromatic ketones.
  • photosensitizers include those selected from the group consisting of methanones, xanthenones, pyrenemethanols, anthracenes, pyrene, perylene, quinones, xanthones, thioxanthones, benzoyl esters, benzophenones, and any combination thereof.
  • photo sensitizers include those selected from the group consisting of [4-[(4- methylphenyl)thio]phenyl]phenyl-methanone, isopropyl-9H-thioxanthen-9-one, 1 -pyrenemethanol, 9-(hydroxymethyl)anthracene, 9, 10-diethoxyanthracene, 9, 10-dimethoxyanthracene, 9, 10- dipropoxyanthracene, 9, 10-dibutyloxyanthracene, 9-anthracenemethanol acetate, 2-ethyl-9, 10- dimethoxyanthracene, 2-methyl-9, 10-dimethoxyanthracene, 2-t-butyl-9,10-dimethoxyanthracene, 2- ethyl-9, 10-diethoxyanthracene and 2-methyl-9, 10-diethoxyanthracene, anthracene, anthraquinones, 2-methylanthraquinone, 2-ethylanth
  • the rubber toughenable base resin may also contain various photoinitiators of different sensitivity to radiation of emission lines with different wavelengths to obtain a better utilization of a UV light source.
  • the use of known photoinitiators of different sensitivity to radiation of emission lines is well known in the art of additive fabrication, and may be selected in accordance with radiation sources of, for example, 351, nm 355 nm, 365 nm, 385 nm, and 405nm. In this context it is advantageous for the various photoinitiators to be selected such, and employed in a concentration such, that equal optical absorption is produced with the emission lines used.
  • the rubber toughenable base resin can include any suitable amount of the
  • photosensitizer for example, in certain embodiments, in an amount up to about 10% by weight of the rubber toughenable base resin, in certain embodiments, up to about 5% by weight of the rubber toughenable base resin, and in further embodiments from about 0.05% to about 2% by weight of the rubber toughenable base resin.
  • free radical photoinitiators are divided into those that form radicals by cleavage, known as “Norrish Type I” and those that form radicals by hydrogen abstraction, known as “Norrish type II".
  • the Norrish type II photoinitiators require a hydrogen donor, which serves as the free radical source.
  • the Norrrish type II photoinitiators are generally slower than Norrish type I photoinitiators which are based on the unimolecular formation of radicals.
  • Norrish type II photoinitiators possess better optical absorption properties in the near-UV spectroscopic region.
  • Photolysis of aromatic ketones such as benzophenone, thioxanthones, benzil, and quinones
  • hydrogen donors such as alcohols, amines, or thiols
  • the photopolymerization of vinyl monomers is usually initiated by the radicals produced from the hydrogen donor.
  • the ketyl radicals are usually not reactive toward vinyl monomers because of the steric hindrance and the derealization of an unpaired electron.
  • the rubber toughenable base resin includes at least one free radical photoinitiator, e.g., those selected from the group consisting of benzoylphosphine oxides, aryl ketones, benzophenones, hydroxylated ketones, 1-hydroxyphenyl ketones, ketals, metallocenes, and any combination thereof.
  • free radical photoinitiator e.g., those selected from the group consisting of benzoylphosphine oxides, aryl ketones, benzophenones, hydroxylated ketones, 1-hydroxyphenyl ketones, ketals, metallocenes, and any combination thereof.
  • the rubber toughenable base resin includes at least one free-radical photoinitiator selected from the group consisting of 2,4,6-trimethylbenzoyl diphenylphosphine oxide and 2,4,6-trimethylbenzoyl phenyl, ethoxy phosphine oxide, /s(2,4,6-trimethylbenzoyl)- phenylphosphineoxide, 2-methyl- 1 -[4-(methylthio)phenyl]-2-morpholinopropanone- 1 , 2-benzyl-2- (dimethylamino)- 1 -[4-(4-morpholinyl) phenyl]- 1 -butanone, 2-dimethylamino-2-(4-methyl-benzyl)-
  • suitable free-radical photoinitiators absorbing in this area include: benzoylphosphine oxides, such as, for example, 2,4,6-trimethylbenzoyl diphenylphosphine oxide (Lucirin TPO from BASF) and 2,4,6-trimethylbenzoyl phenyl, ethoxy phosphine oxide (Lucirin TPO-L from BASF), £zs(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irgacure 819 or BAPO from Ciba), 2-methyl-l-[4-(methylthio)phenyl]-2-mo holinopropanone-l (Irgacure 907 from Ciba), 2-benzyl-2-(dimethylamino)-l-[4-
  • photosensitizers are useful in conjunction with photoinitiators in effecting cure with LED light sources emitting in this wavelength range. Examples of suitable
  • photosensitizers include: anthraquinones, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2- tertbutylanthraquinone, 1-chloroanthraquinone, and 2-amylanthraquinone, thioxanthones and xanthones, such as isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and 1- chloro-4-propoxythioxanthone, methyl benzoyl formate (Darocur MBF from Ciba), methyl-2- benzoyl benzoate (Chivacure OMB from Chitec), 4-benzoyl-4'-methyl diphenyl sulphide
  • UV radiation sources It is possible for UV radiation sources to be designed to emit light at shorter
  • wavelengths For light sources emitting at wavelengths from between about 100 and about 300 nm, it is possible to employ a photosensitizer with a photoinitiator. When photosensitizers, such as those previously listed are present in the formulation, other photoinitiators absorbing at shorter wavelengths can be used.
  • photoinitiators include: benzophenones, such as benzophenone, 4-methyl benzophenone, 2,4,6-trimethyl benzophenone, dimethoxybenzophenone, and 1-hydroxyphenyl ketones, such as 1-hydroxycyclohexyl phenyl ketone, phenyl (1- hydroxyisopropyl)ketone, 2-hydroxy-l-[4-(2-hroxy ethoxy) phenyl]-2-methyl-l-propanone, and 4- isopropylphenyl(l-hydroxyisopropyl)ketone, benzil dimethyl ketal, and oligo-[2-hydroxy-2-methyl- l-[4-(l-methylvinyl)phenyl] propanone] (Esacure KIP 150 from Lamb erti).
  • benzophenones such as benzophenone, 4-methyl benzophenone, 2,4,6-trimethyl benzophenone, dimethoxybenzophenone
  • Radiation sources can also be designed to emit at higher wavelengths.
  • suitable free radical photoinitiators include: camphorquinone, 4,4'- bis(diethylamino) benzophenone (Chivacure EMK from Chitec), 4,4'-bis(N,N'-dimethylamino) benzophenone (Michler's ketone), bis(2,4,6- trimethylbenzoyl)-phenylphosphineoxide (“BAPO,” or Irgacure 819 from Ciba), metallocenes such as bis (eta 5-2-4-cyclopentadien-l-yl) bis [2,6-difluoro-3-(lH-pyrrol-l-yl) phenyl] titanium
  • H-Nu 470 H-Nu-535, H-Nu-635, H-Nu-Blue-640, and H-Nu-Blue-660.
  • the light emitted by the radiation source is UVA radiation, which is radiation with a wavelength between about 320 and about 400nm.
  • the light emitted by the radiation source is UVB radiation, which is radiation with a wavelength between about 280 and about 320nm.
  • the light emitted by the radiation source is UVC radiation, which is radiation with a wavelength between about 100 and about 280nm.
  • the rubber toughenable base resin can include any suitable amount of the free-radical photoinitiator as component, for example, in certain embodiments, in an amount up to about 10 wt% of the rubber toughenable base resin, in certain embodiments, from about 0.1 to about 10 wt% of the rubber toughenable base resin, and in further embodiments from about 1 to about 6 wt% of the rubber toughenable base resin.
  • the rubber toughenable base resin further contains customary additives.
  • Customary additives to the rubber toughenable base resin may include without limitation stabilizers, fillers, dyes, pigments, antioxidants, wetting agents, chain transfer agents such as polyols, leveling agents, defoamers, surfactants, bubble breakers, acid scavengers, thickeners, flame retardants, silane coupling agents, ultraviolet absorbers, resin particles, core-shell particle impact modifiers, and the like.
  • Such components may be added in known amounts and to desired effect.
  • Stabilizers are often added to the rubber toughenable base resin in order to further prevent a viscosity build-up, for instance a viscosity build-up during usage in a solid imaging process.
  • Useful stabilizers include those described in, e.g., U.S. Pat. No. 5,665,792.
  • the presence of a stabilizer is optional.
  • the liquid radiation curable resin composition for additive fabrication comprises from 0.1 wt% to 3% of a stabilizer.
  • stabilizers are usually hydrocarbon carboxylic acid salts of group IA and IIA metals. Most preferred examples of these salts are sodium bicarbonate, potassium bicarbonate, and rubidium carbonate. Solid stabilizers are generally not preferred in filled resin compositions. Alternative stabilizers include polyvinylpyrrolidones and polyacrylonitriles.
  • Fillers are often added to radiation curable compositions for additive fabrication to impart increased strength, rigidity and modulus. Useful fillers include those described in, e.g. U.S. Pat. No. 9,228,073, assigned to DSM IP Assets, B.V. Also described in the '073 patent are useful prescriptions for stabilized matrices comprising more than one filler type which may be followed to impart a filled matrix with improved resistance to filler particle precipitation.
  • Core-shell particles are also often added to radiation curable compositions for additive fabrication to impart increased toughness.
  • Useful core-shell particles include those described in, e.g. publication of patent application number US20100304088, assigned to DSM IP Assets, B.V.
  • base resin matrices with a crosslink density that falls within certain ranges will readily toughen when combined with the liquid phase-separating toughening agents prescribed herein, and further surprisingly exhibit a tendency to largely maintain the concomitant HDT values, in contravention of the longstanding principle of the known inverse relationship between toughness and HDT.
  • compositions according to the current invention exhibit an increase in elongation at break of at least 5%, more preferably at least 20%, more preferably at least 30%, more preferably at least 50%, and in some embodiments at least 100%, all while maintaining an HDT value of within 7 degrees, more preferably 5 degrees, more preferably 3 degrees, more preferably within 1 degree when compared to compositions with incompatible rubber toughenable base resin matrices, or those not including such liquid phase- separating toughening agents.
  • Mc molecular weight between crosslinks
  • Mc values may be derived in different ways.
  • One experimental method involves a derivation based upon data evidencing a network's elongation.
  • ideal Mc values are derived by calculations based upon the nature of the individual components of a formulation, along with such components' individual molecular weights and functionalities.
  • a formula for calculating such ideal Mc values of a cured network taken from James Mark "Physical Properties of Polymers" 3rd Edition, Cambridge University Press, 2004, P. 11-12, is as follows:
  • Mc molecular weight between cross-links (in g/mol)
  • V volume of network (in cc)
  • ⁇ total For the network, calculate ⁇ for each component and sum the values accordingly.
  • a demonstration of ⁇ may be derived by way of example by presupposing a resin with a 4-functional component as the only crosslinker (remaining species are difunctional and so they only connect and extend the junction cross-link points) with a molecular weight of 252 g/mol which is further present in an amount relative to the entire composition with which it is associated of 35 wt% (35 grams out of 100 grams).
  • the ⁇ for this component, (and thus the entire network since this is the only cross-linker molecule), would therefore be calculated as follows:
  • Mc values according to the present invention can be derived.
  • compatible rubber toughenable base resin possess an Mc value of at least 130 g/mol, more preferably greater than 150 g/mol. In another embodiment, compatible rubber toughenable base resins possess an Mc value of at least 160 g/mol; and in another embodiment greater than 180 g/mol.
  • the Mc of a compatible rubber toughenable base resin is less than 2,000 g/mol, more preferably less than 1,000 g/mol, more preferably less than 500 g/mol, more preferably less than 400 g/mol, more preferably less than 300 g/mol, more preferably less than 280 g/mol, more preferably less than 260 g/mol, more preferably less than 230 g/mol, more preferably less than 200 g/mol. If the Mc value of the rubber
  • toughenable base resin becomes too low, the highly crosslinked network does not readily toughen even upon the addition of liquid phase-separating toughening agents. If the Mc value is too high, on the other hand, the polymer network of the base resin itself is not sufficiently crosslinked to enable the general properties (modulus, HDT) necessary to form for suitability in many end-use applications common of components created via additive fabrication processes.
  • Radiation curable compositions for additive fabrication with improved toughness also possess at least one liquid, phase-separating toughening agent.
  • Such agents are liquid at room temperature and are typically soluble within the base resin prior to cure. Then, upon curing of the entire radiation curable composition into which they are incorporated, the toughening agents phase- separate forming in-situ rubbery domains residing in the interstitial spaces within the crosslink matrix formed by the surrounding thermoset polymer. These phase domains may be light refractive or not, depending on their size and refractive index relative to the remainder of the polymer matrix. If they are sufficiently sized and light refractive, they will impart a white color to the final cured product.
  • phase domains are an important indicator of the relative amount of simultaneous improved rubber toughenability and heat resistance imparted in the corresponding cured object (when compared to the base resin matrix alone), particularly when such phase domains are added to compatible base resin matrices as prescribed elsewhere herein.
  • Inventors have surprisingly found that such rubber toughenability and heat resistance are particularly optimized if the liquid phase- separating toughening agents are selected such that they are configured to yield average phase domains of at least 2 microns and less than 25 microns, more preferably from about 5 microns to about 20 microns, or from about 7 microns to about 15 microns, when measured according to the average phase domain size procedure outlined in the following paragraph.
  • liquid phase-separating toughening agents can impart a substantial toughening affect upon the cured composition, without a substantial sacrifice in the cured composition's heat deflection temperature, as is known to occur with existing reagents and methods for improving toughness into radiation curable compositions for additive fabrication.
  • the liquid phase-separating toughening agent when incorporated into a sufficiently compatible rubber toughenable base resin matrix as described above, can be a high molecular weight dimer fatty acid polyol.
  • the high molecular weight dimer fatty acid polyol possesses a molecular weight of greater than 2000 g/mol, more preferably 3000 g/mol, more preferably greater than 4000 g/mol. In another embodiment, such polyol possesses a molecular weight of 8000 g/mol. In an embodiment, the high molecular weight dimer fatty acid polyol possesses a molecular weight of up to 10,000 g/mol.
  • the high molecular weight dimer fatty acid polyol is a propylene oxide or ethylene oxide.
  • high liquid phase-separating toughening agents includes high molecular weight polyols such as the Acclaim series of polypropylene glycols with varying molecular weight, such as Acclaim 4200 and 8200, as well as Croda epoxy-functional toughening agents such as B-tough A2 and Beta Tough 2CR. Also suitable for use from Croda as such a liquid-phase separating toughening agent are the PriplastTM series polyester polyols.
  • a second aspect of the claimed invention is a radiation curable composition for additive fabrication with improved toughness comprising:
  • a rubber toughenable base resin further comprising
  • liquid phase-separating toughening agent is an epoxidized pre-reacted hydrophobic macromolecule.
  • Liquid phase-separating toughening agents which are pre-reacted epoxidized hydrophobic macromolecule s
  • the radiation curable compositions for additive fabrication with improved toughness incorporate at least one liquid phase- separating toughening agent which is an epoxidized, pre- reacted, hydrophobic macromolecule.
  • epoxidized means that such toughening agent is epoxy-functional; that is, it is able to undergo a ring-opening reaction of one or more epoxy moieties present anywhere on its molecule. Such moieties need not be terminating epoxy groups.
  • Pre-reacted for purposes herein means that such epoxidization and/or
  • the epoxidized pre-reacted hydrophobic macromolecule is a triblock copolymer possessing terminating epoxy- or acrylate- functional hard blocks and at least one immiscible soft block.
  • the triblock copolymer is formed by the reaction product of a soft-block originator with a monofunctional anhydride, and then further reacting an epoxy- functional reactant.
  • the soft-block originator is selected from the group consisting of polybutadienes, polyols, and polydmethylsiloxanes, and any combination thereof, although other known soft-block originators and combinations may be used.
  • the monofunctional anhydride is an hexahydropthalic anhydride because it possesses a known superior water stability, but any monofunctional anhydrides may be used as is suitable.
  • the epoxidized pre-reacted hydrophobic macromolecule is derived from a triglyceride fatty acid or a tall oil.
  • Certain non- limiting preferred tall oils include vegetable-based oils such as soybean or linseed oil, along with any of the drying oils such as linseed, tung, poppy seed, walnut, and rapeseed oil, to name a few.
  • the epoxidized pre-reacted hydrophobic macromolecule is derived from a compound of the following formula:
  • Ri, R 2 , and R 3 are the same or different, and are each a C4-C50 unsaturated alkyl chain, wherein the unsaturation has been at least 2% epoxidized, more preferably 10% epoxidized, more preferably 30% epoxidized.
  • the epoxidized pre- reacted hydrophobic macromolecule is derived from the an epoxidized soybean oil (ESO), such as the following:
  • the epoxidized triglyceride or tall oil is reacted with an alkyl chain carboxylic acid to form a pre-reacted hydrophobic macromolecule.
  • the synthesis of epoxidized pre-reacted hydrophobic macromolecules according to the present invention are carried out in the presence of various catalysts. Any suitable catalysts known in the art could be used, especially weak base or chromium-base catalysts. In an embodiment, the catalyst used to enable to formation of the pre-reacted hydrophobic macromolecule is
  • triphenylphosphine available from Sigma Aldrich, or a chromium catalyst, such as the commercial product AMC-2 from AMP AC Fine Chemicals.
  • the ratio of equivalents utilized in the synthesis of the epoxidized pre-reacted hydrophobic macromolecule is 1 part epoxidized triglyceride or tall oils to 2 part alkyl chain carboxylic acids. In another embodiment, that ratio is 1 :3. In other embodiments, the epoxidized pre-reacted hydrophobic macromolecule is synthesized by reacting, in terms of equivalents, a ratio of ESO to an alkyl chain carboxylic acid from about 2:3 to about 2:7, more preferably from about 1 :2 to about 1 :3.
  • the ratios and reagents are maintained within limits to ensure an appropriate length of the alkyl chain attached to the triglyceride or tall oil. This is because it is believed that the alkyl chain's length turn directly affects the macromolecule' s hydrophobicity. Thus if the alkyl chain becomes too long, the macromolecule becomes too hydrophobic and will not readily react with the surrounding rubber toughenable base resin matrix. If it becomes too short, on the other hand, it may not possess the requisite hydrophobicity to phase-separate from the matrix.
  • the epoxidized pre-reacted hydrophobic macromolecules of the present invention can optionally be further acrylate functionalized prior to incorporation in the rubber toughenable base resin. This can occur, by for example, acrylate-functionalizing the alkyl chain carboxylic acid prior to the reaction with the epoxidized triglyceride or tall oil in the presence of a suitable catalyst to yield an acrylate-functionalized epoxidized pre-reacted hydrophobic macromolecule. Especially, when this has occurred, the accompanying rubber toughenable base resin need not necessarily contain cationically curable components.
  • liquid phase-separating toughening agent is an acrylate functionalized pre-reacted hydrophobic macromolecule
  • components (1) and (3) namely, the cationically polymerizable component and cationic photoinitiator, respectively, are not present in the composition. Regardless, the
  • a liquid phase-separating toughening agent's solubility within its associated rubber toughenable base resin is of significant importance when ensuring optimum usefulness therewith.
  • the solubility delta of the liquid phase-separating toughening agent and its associated rubber toughenable base resin is within certain ranges, the toughness of the resulting cured three-dimensional articles are improved, and the heat resistance is sufficiently maintained.
  • this factor along with the aforementioned Mc values of the corresponding rubber toughenable base resin, enable the skilled artisan to select optimally compatible compositional substituents that impart superior toughness and heat resistance properties into the three-dimensional objects cured therefrom.
  • solubility "deltas” can be expressed by using the Hansen solubility parameters (HSP).
  • HSP Hansen solubility parameters
  • the deltas expressed herein would represent the theoretical straight-line distance in the three dimensional Hansen space between the rubber toughenable base resin and the liquid phase-separating toughening agent. According to a preferred embodiment, the deltas are from about 10 to about 25, in another embodiment from 10-15, in another embodiment from 15-20, in another embodiment from 20-25.
  • a third aspect of the claimed invention is a process of forming a three-dimensional object comprising the steps of forming and selectively curing a liquid layer of the radiation curable composition for additive fabrication with improved toughness according to either the first or second aspects of the claimed invention with actinic radiation and repeating the steps of forming and selectively curing the liquid layer of the radiation curable composition for additive fabrication according to the first or second aspects of the claimed invention a plurality of times to obtain a three-dimensional object.
  • a fourth aspect of the claimed invention is the three-dimensional object formed by the process according to the third aspect of the claimed invention from the radiation curable
  • composition for additive fabrication with improved toughness according to either the first or second aspects of the claimed invention.
  • Table 1 describes the various commercially available raw materials which constitute various components or subcomponents, as the case may be, of the radiation curable compositions for additive fabrication with improved toughness used in the present examples.
  • Table 2 describes the synthesis of the liquid hydrophobic macromolecular phase- separating toughening agents which are not commercially available and are used in the present examples.
  • Triblock copolymer "ABA" type hydrophobic macromolecular phase separating toughening agents were generally synthesized from hydrophobic center "B” blocks end-capped with polar and reactive "A” blocks. To connect B with A, an anhydride small molecule was used as linker. A typical synthetic procedure was as follows. To a 3-neck round bottom flask equipped with thermometer and mechanical stirrer was added 1 equivalent (X moles) of the hydrophobic center "B” oligomer block with -OH end group functionality. With gentle stirring, 2 equivalents (2X moles) of a monoanhydride, i.e. HHP A, was added along with 0.1 wt% of base catalyst (DABCO).
  • DABCO base catalyst
  • This mixture was heated typically to 80 °C for several hours (typically 2 hours, but as long as 4 hours to ensure complete coupling of hydroxyl groups with anhydrides, forming carboxylic acid end group functional oligomers).
  • diepoxide end "A" block was added to this same vessel.
  • Typical excess used was 5 equivalents (moles) of diepoxide monomer per 1 equivalent (mole) of hydrophobic center block oligomer. Since the molecular weight of the center block was in most cases much greater than the molecular weight of the diepoxide end blocks, the actual mass excess of free diepoxide after complete reaction was minimal.
  • the acid+epoxy coupling catalyst was also added at 0.1 wt%; typical catalyst used was triphenylphosphine (TPP) but other catalysts such as the AMC-2 or other chromium catalysts are effective for this coupling reaction as well.
  • TPP triphenylphosphine
  • the mixture was then heated to 105 °C for 5 to 6 hours with gentle stirring. At this time, a small aliquot of sample was taken from the reaction and analyzed for acid value (A. V.) using a Metrohm 751 GPD Titrino potentiometric titration system. If A.V. was sufficiently low corresponding to >95% consumption of carboxylic acid groups, the product was poured off and stored. If not, reaction was continued and sampled periodically for A. V. until reaction completion was obtained.
  • Examples 1-5 and 42-47 represent three-dimensional components which were created in accordance with ASTM D638-10. Examples 6-41 were used by evaluating draw-down strips, which were created by the procedure described below.
  • a sheet of flexible Mylar PET (4 mil thick) was taped to the top of a glass plate.
  • the tensile bar strips were gently removed by bending the Mylar film and peeling the strips away. The strips were then turned over and UV post cured for another 30 minutes.
  • strips were then thermally post cured using procedures used for thermally post curing 3D parts in this work (i.e. 2 hours, 100 °C).
  • Samples were tested in accordance with ASTM D638-10, except as modified as described herein. Samples were built by a Viper SLA machine (S/N 03FB0244 or S/N 02FB0160), manufactured by 3D Systems, Inc., to the standard, art-recognized Type I "dogbone" shape with an overall length of 6.5 inches, an overall width of 3/4 of an inch (0.75 inches), and an overall thickness of 1/8 of an inch (0.125 inches). Samples were conditioned for 7 days at 23°Celsius at 50% relative humidity. The conditioning period exceeds the minimum prescribed in the ASTM 618-13 standard to ensure maximum stabilization in the cationic cure of the hybrid system.
  • the samples were measured and then placed in the Sintech tensile-tested S/N using the 6500 N load cell S/N # with a 50% extensometer SN#.
  • the speed of testing was set at 5. lmm/min with a nominal strain rate of 0.1 mm/min at the start of test.
  • the Young's modulus or Modulus of Elasticity was calculated by extending the initial linear portion of the load-extension curve and dividing the difference in stress corresponding to any segment of the section on this straight line by the corresponding difference in strain. All elastic modulus values were computed using the average original cross sectional area in the gage length segment of the specimen in the calculations.
  • the Percent Elongation at break was calculated by reading the extension at point of specimen rapture and dividing that extension by the original gage length and multiplying by 100. Standard deviations were calculated according to known statistical methods.
  • Heat Deflection Temperature is tested on parts built, washed, and UV postcured, as previously described. Specimens are numbered and allowed to condition at 23° C, 50% relative humidity for a period of not less than 48 hours. Part dimensions and test method is as described in ASTM D648-00a Method B. Reported HDT values are for an applied stress of 0.45 MPa (66 psi). Care was taken to ensure that the test contacts for the HDT tester were in contact with smooth surfaces of the polymer part. It has been found that surface irregularities (i.e. non-smooth surfaces) can contribute to a lower HDT than measuring a smooth part surface. Top surfaces of HDT parts are typically smooth without alteration. Sidewalls and bottom- facing surfaces were sanded with 100 grit followed by 250 grit sandpaper to ensure a smooth testing surface before measurement. Listed HDT data are for parts that have not experienced thermal postcure.
  • the measuring container was a H-Z3/SM cup (diameter 27.110mm) which was filled with 21.4 grams of sample (enough to the spindle). Measurements were recorded in millipascal-seconds (mPa s), but converted and reported herein as centipoise (cPs).
  • Izod impact tests of specimen were tested according to ASTM D256A. Parts were built by a Viper SLA machine (S/N 03FB0244 or S/N 02FB0160) manufactured by 3D Systems, Inc. to the standing testing size according to ASTM D256A. Specimen were conditioned for at least 48 hours at 23° Celsius at 50% relative humidity after a thermal post-cure. The specimen were then notched with a Qualitest saw. They were then tested on a Zwick/Roell HIT5.5P instrument, using an Izod Hammer of 2.75J. The average of at least 5 test specimens is reported.
  • a first aspect of a first additional exemplary embodiment of the invention is a radiation curable composition for additive fabrication with improved toughness comprising:
  • a rubber toughenable base resin further comprising
  • liquid phase-separating toughening agent is present in an amount, relative to the weight of the rubber toughenable base resin, in a ratio from about 1 :99 to about 1 :3, more preferably about 1 :99 to about 1 :4, more preferably about 1 :99 to about 1 :9, more preferably about 1 :50 to about 1 : 12, more preferably about 1 : 19; and
  • the average molecular weight between crosslinks (Mc) of the rubber toughenable base resin is greater than 130 g/mol, more preferably greater than 150 g/mol; in another embodiment more preferably greater than 160 g/mol; and in another embodiment greater than 180 g/mol.
  • An additional aspect of the first additional exemplary embodiment is a radiation curable composition for additive fabrication with improved toughness according to any of the previous aspects of the first additional exemplary embodiment, wherein the liquid phase- separating toughening agent is a high molecular weight dimer fatty acid polyol.
  • An additional aspect of the first additional exemplary embodiment is a radiation curable composition for additive fabrication with improved toughness according to any of the previous aspects of the first additional exemplary embodiment, wherein the high molecular weight polyol is selected to be configured to form, after curing of the radiation curable composition, phase domains with an average size of from about 2 microns to about 25 microns, or from about 5 microns to about 20 microns, or from about 7 microns to about 15 microns, when measured according to an Average Phase Domain Size Procedure.
  • An additional aspect of the first additional exemplary embodiment is a radiation curable composition for additive fabrication with improved toughness according to any of the previous aspects of the first additional exemplary embodiment, wherein the high molecular weight dimer fatty acid polyol possesses a molecular weight of greater than 2000 g/mol, more preferably 3000 g/mol, more preferably greater than 8000 g/mol.
  • An additional aspect of the first additional exemplary embodiment is a radiation curable composition for additive fabrication with improved toughness according to any of the previous aspects of the first additional exemplary embodiment, wherein the high molecular weight dimer fatty acid polyol is a propylene oxide or ethylene oxide.
  • An additional aspect of the first additional exemplary embodiment is a radiation curable composition for additive fabrication with improved toughness according to any of the previous aspects of the first additional exemplary embodiment, wherein Mc of the rubber toughenable base resin is less than 500 g/mol, more preferably less than 400 g/mol, more preferably less than 300 g/mol, more preferably less than 280 g/mol, more preferably less than 260 g/mol, more preferably less than 230 g/mol, less than 200 g/mol.
  • An additional aspect of the first additional exemplary embodiment is a radiation curable composition for additive fabrication with improved toughness according to any of the previous aspects of the first additional exemplary embodiment, wherein a three-dimensional component created therefrom by means of an additive fabrication process yields an elongation value that is at least 20% greater, more preferably at least 50% greater, more preferably 100% greater than a corresponding elongation value of a three dimensional component created from the constituent rubber toughenable base resin of said radiation curable composition.
  • An additional aspect of the first additional exemplary embodiment is a radiation curable composition for additive fabrication with improved toughness according to any of the previous aspects of the first additional exemplary embodiment, wherein a three-dimensional component created therefrom by means of an additive fabrication process yields an HDT value that is within at least 5 degrees, more preferably within at least 3 degrees, more preferably within at least 1 degree Celsius of a corresponding elongation value of a three dimensional component created from the constituent rubber toughenable base resin of said radiation curable composition.
  • a first aspect of a second additional exemplary embodiment is a radiation curable composition for additive fabrication with improved toughness comprising:
  • a rubber toughenable base resin further comprising
  • liquid phase-separating toughening agent a liquid phase-separating toughening agent; wherein the liquid phase-separating toughening agent is an epoxidized pre-reacted hydrophobic macromolecule.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the average molecular weight between crosslinks (Mc) of the rubber toughenable base resin is greater than 130 g/mol, more preferably greater than 150 g/mol; in another embodiment more preferably greater than 160 g/mol; and in another embodiment greater than 180 g/mol;
  • Mc of the rubber toughenable base resin is less than 500 g/mol, more preferably less than 400 g/mol, more preferably less than 300 g/mol, more preferably less than 280 g/mol, more preferably less than 260 g/mol, more preferably less than 230 g/mol, less than 200 g/mol.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the rubber toughenable base resin further contains less than 50%, more preferably less than 40%, more preferably less than 30% by weight, relative to the entire weight of the rubber toughenable base resin, of an aromatic glycidyl epoxy.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the glycidyl epoxy is a bisphenol A diglycidyl ether.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the rubber toughenable base resin further comprises a polyol component.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the polyol component is present in an amount, relative to the entire weight of the rubber toughenable base resin, of at least about 3%, more preferably at least 5%, more preferably 10%.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule is a triblock copolymer possessing terminating epoxy- or acrylate- functional hard blocks; and
  • At least one immiscible soft block At least one immiscible soft block.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the triblock copolymer is formed by the reaction product of a soft-block originator with a mono functional anhydride such as
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the soft-block originator is selected from the group consisting of polybutadienes, polyols, and polydmethylsiloxanes, and any combination thereof.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the polyols are selected from the group consisting of polyethylene oxide and polypropylene oxide.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxy-functional reactant is selected from the group consisting of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane-l,4-dioxane, bis(3,4- epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, vinylcyclohexene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6- methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, ⁇ -caprolactone
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule is derived from a triglyceride fatty acid.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule is derived from a tall oil.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized tall oil is an epoxidized vegetable oil, such as soybean or linseed oil.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule is derived from a compound of the following formula:
  • Ri, R2, and R3 are the same or different, and are each a C4-C50 unsaturated alkyl chain, wherein the unsaturation has been at least 10% epoxidized, more preferably 30% epoxidized.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule is derived from the following compound:
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule is the reaction product of an epoxidized soybean oil (ESO) and an alkyl chain carboxylic acid, thereby forming an ESO-based globular toughener.
  • ESO epoxidized soybean oil
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule is synthesized in the presence of a catalyst.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the catalyst is selected from the group consisting of triphenylphosphine, chromium, or DABCO catalysts.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the alkyl chain carboxylic acid is liquid at room temperature.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule is synthesized by reacting, in terms of equivalents, a ratio of the ESO to the alkyl chain carboxylic acid from about 2:3 to about 2:7, more preferably from about 1 :2 to about
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the alkyl chain carboxylic acid is selected from the group consisting of isopalmitic acid, 2-hexyl decanoic acid, and compounds of the following structure:
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the alkyl chain carboxylic acid possesses the following structure:
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule possesses the following structure:
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule possesses a molecular weight of from about 800 g/mol to about 4000 g/mol, more preferably from about 1000 g/mol to about 2500 g/mol, more preferably from about 1500 g/mol to about 2000 g/mol.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule is further acrylate functionalized.
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the wherein epoxidized pre-reacted hydrophobic macromolecule that is further acrylate functionalized possesses the following structure:
  • An additional aspect of the second additional exemplary embodiment is a radiation curable composition for additive fabrication according to any of the previous aspects of the second additional exemplary embodiment, wherein the epoxidized pre-reacted hydrophobic macromolecule is present, relative to the weight of the entire composition, in an amount from about 1% to about 20%, more preferably from about 1.5% to about 12%, more preferably from about 2% to about 10%, more preferably about 5%.
  • a first aspect of a third additional exemplary embodiment is a process of forming a three-dimensional object comprising the steps of forming and selectively curing a liquid layer of the radiation curable composition for additive fabrication with improved toughness of any of the aspects of either of the first or second additional exemplary embodiments of the invention with actinic radiation and repeating the steps of forming and selectively curing the liquid layer of the radiation curable composition for additive fabrication a plurality of times to obtain a three- dimensional object.
  • An additional aspect of the third additional exemplary embodiment is the three- dimensional object formed by the process of the first aspect of the third additional exemplary embodiment from the radiation curable composition for additive fabrication with improved toughness of any the aspects of either the first or second additional exemplary embodiments of the invention.
  • An additional aspect of the third additional exemplary embodiment is the three- dimensional object of the previous aspect of the third additional exemplary embodiment wherein the elongation value is at least 5%, more preferably at least 10%, more preferably at least 20%, more preferably at least 50%, and/or the HDT value is at least 75, more preferably at least 85, more preferably at least 95 degrees Celsius.

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Abstract

La présente invention concerne des compositions durcissables par un rayonnement pour la fabrication additive. De telles résines comprennent une formule de résine de base de renforcement de caoutchouc et un agent de renforcement liquide de séparation des phases. La résine de base de renforcement de caoutchouc, qui peut posséder un poids moléculaire moyen suffisamment élevé entre des réticulations et peut être une macromolécule hydrophobe ayant subi une réaction préalable, peut en outre comprendre un constituant polymérisable par voie cationique, un constituant polymérisable par voie radicalaire, un photo-initiateur cationique, un photo-initiateur à radicaux liquides et des additifs habituels. L'invention concerne également des procédés pour former des objets tridimensionnels à l'aide de telles compositions durcissables par rayonnement pour une fabrication additive présentant une ténacité améliorée, conjointement avec les pièces tridimensionnelles créées à partir de celles-ci.
PCT/US2017/022311 2016-03-14 2017-03-14 Compositions durcissables par un rayonnement pour la fabrication additive présentant une ténacité améliorée et une résistance à la température élevée WO2017160845A1 (fr)

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